CN110483460A - A kind of preparation method of 3- seleno coumarin kind compound - Google Patents
A kind of preparation method of 3- seleno coumarin kind compound Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
- C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
- C07D311/12—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 3 and unsubstituted in position 7
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
- C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
- C07D311/14—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 6 and unsubstituted in position 7
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/06—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2
- C07D311/08—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring
- C07D311/16—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms directly attached in position 2 not hydrogenated in the hetero ring substituted in position 7
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/04—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring
- C07D311/42—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms in positions 2 and 4
- C07D311/56—Benzo[b]pyrans, not hydrogenated in the carbocyclic ring with oxygen or sulfur atoms in positions 2 and 4 without hydrogen atoms in position 3
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D311/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings
- C07D311/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only hetero atom, condensed with other rings ortho- or peri-condensed with carbocyclic rings or ring systems
- C07D311/78—Ring systems having three or more relevant rings
- C07D311/92—Naphthopyrans; Hydrogenated naphthopyrans
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- C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
- C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
- C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
Abstract
The invention discloses a kind of preparation methods of 3- seleno coumarin kind compound, comprising: is oxidant with PIFA in DCM solvent, using coumarin kind compound and selenide compounds as substrate, synthesizes 3- seleno coumarin kind compound at room temperature.Reaction raw materials of the present invention are cheap and easy to get, and preparation method is simple, make oxidant with PIFA, and reaction cost is low, and the reaction time is short, and yield is high, easy to operate, the synthesis suitable for different types of 3- seleno coumarin kind compound.The method of the present invention can be used for synthesizing a series of 3- seleno coumarin kind compound, and the product of synthesis can be used as intermediate compound, for further constructing complicated reactive compound；Such compound has great pharmaceutical activity potentiality simultaneously.
Description
Technical field
The invention belongs to organic synthesis fields, and in particular to one kind prepares 3- seleno tonka-bean by regioselectivity selenizing
The method of chlorins compound.
Background technique
Cumarin and its derivative are distributed widely in natural products and pharmaceutical activity molecule as core skeleton.Meanwhile
Due to the optical activity of such compound, they play an important role in organic material.In numerous coumarin derivatives
In, 3- substituted cumarin compound is living due to being proven to have a series of biologies such as anti-inflammatory, anti-oxidant, AntiHIV1 RT activity, anticancer, antibacterial
Property and have received widespread attention.Since 3- substituted cumarin class compound is in the important application of different field, such compound
Synthetic method obtained extensive exploration.
The reactant coupling of pre-functional group is the conventional method for preparing 3- substituted cumarin.In recent years, directly hydrocarbon
Key functional group is turned to a kind of direct, Atom economy synthetic strategy, is widely used in modern organic synthesis.Based on this
One strategy, many methods for introducing functional group at three, cumarin carbon that regioselectivity is coupled by intersecting dehydrogenation are established.
Two classes can be divided into according to the method for reaction mechanism, these reports.One kind is related to the electrophilic attack cumarin carbon of palladium complex ion
Three.Under normal conditions, this kind of reaction needs additional additive and ligand, they are fragrant for 3- aryl-coumarin, 3- alkenyl
The synthesis of legumin and 3- phosphinylidyne butylcoumariii.Another kind of reaction is related to three, the electrophilic attack cumarin carbon of free radical.This kind of reaction
Metallic catalyst (cobalt, copper, iron), excessive oxidant and high temperature is needed to generate free radicals, for synthesizing 3- alkyl cumarin, 3-
Benzyl cumarin and 3- aroyl cumarin.Recently, Deng study group and Yang study group have developed respectively in cumarin carbon three
The method that position introduces difluoromethyl and alkyl, this method are completed by photocatalysis at room temperature.It will be apparent that development environment close friend's item
Under part, in three formation new keys of cumarin carbon, the especially method of heteroatoms key is very urgent and important.
Selenium is very important a kind of element in human body, and selenium-containing compound is distributed widely in bioactive molecule and natural production
In object.Up to the present, it is developed for constructing carbon selenium key there are many method, they are using elemental selenium or non-elemental selenium as selenium
Change reagent.However, the method in relation to three selenizings of cumarin carbon is then seldom reported.Only it can be used for cumarin carbon three there are three types of method
Position selenizing, but they are only applicable to four, the carbon cumarins with substituent group.As far as we know, it there is no direct regional choice at present
The method in three selenizings of coumarin skeleton carbon of property.Therefore, develop the regioselectivity direct at room temperature that PIFA promotes
It is just particularly important and urgently in the method for three selenizings of cumarin carbon.The foundation of this method not only has in synthesis chemistry
Important meaning and value；It will further facilitate comprehensive research of 3- seleno coumarin kind compound bioactivity, discovery simultaneously
New pharmaceutical active compounds.
Summary of the invention
The present invention provides one kind with PIFA (two (trifluoroacetyl oxygroup) iodobenzenes) as oxidant, is with cumarin and selenide
The method of the direct synthesis 3- seleno coumarin kind compound of raw material, this method raw material are easy to get, and preparation method is simple.
A kind of preparation method of 3- seleno coumarin kind compound, comprising: be oxidation with PIFA at room temperature in a solvent
Agent, cumarin and selenide are reacted, and obtain the 3- seleno cumarin after post treatment after reaction；
Shown in the structure such as formula (I) of the 3- seleno cumarin:
Shown in the structure of the coumarin kind compound such as formula (II):
Shown in the structure of the selenide compounds such as formula (III):
In formula (I)~(III), R1Hydrogen, C1~C4Alkyl, C1~C4Alkoxy, acyloxy, nitro, phenyl or halogen；
R2For hydrogen, C1~C4Alkyl, C1~C4Alkoxy, nitro or halogen；
X is N or C；
The representation of dotted portion may exist, can partially in the presence of or be completely absent.
Specifically, the structural formula of the 3- seleno cumarin is as follows:
In formula (IV), R1For hydrogen, C1~C4Alkyl, C1~C4Alkoxy, acyloxy, nitro, phenyl or halogen；Formula (VII)
In, R2For hydrogen, C1~C4Alkyl, C1~C4Alkoxy, nitro or halogen.
Shown in the structure of the coumarin kind compound such as formula (X)~(XII):
In formula (X), R1For hydrogen, C1~C4Alkyl, C1~C4Alkoxy, acyloxy, nitro, phenyl or halogen.
The selenide compounds have the structure of chemical formula (XIII)~(XV):
In formula (XIII), R2For hydrogen, C1~C4Alkyl, C1~C4Alkoxy, nitro or halogen.
Preferably, the oxidant is PIFA, the oxidant of other types, including iodobenzene diacetate (PIDA), 2- iodine
Acyl group benzoic acid (IBX), tert-butyl hydroperoxide (TBHP), sodium peroxydisulfate generate reaction without product.
The molar ratio of the coumarin kind compound and the selenide compounds are as follows: 1:1.2, to improve reaction
Yield.The amount for reducing selenide can be such that reaction yield reduces.
The molar ratio of the coumarin kind compound and the oxidant PIFA is 1:1, to improve the yield of reaction.
The amount for reducing oxidant can be such that reaction yield reduces.
Reaction dissolvent is DCM, and the solvent of other types, including polar solvent and nonpolar solvent reduce reaction yield
Or it is generated without product.
The reaction equation of the synthesis are as follows:
Preferably, R1For hydrogen, methyl, methoxyl group, acetoxyl group, nitro, phenyl, F, Cl or Br；R2For hydrogen, methyl,
Methoxyl group, nitro, F, Cl or Br.
The synthetic reaction principle are as follows: PIFA is reacted with diphenyl selenide generates phenylseleno free radical and trifluoroacetyl oxygroup iodine
Benzene radical.Three generation seleno free radical intermediates of the electrophilic attack cumarin carbon of phenylseleno free radical.The free radical is by trifluoro
Acetoxyl group iodobenzene free-radical oxidation generates seleno cationic intermediates.Cationic intermediates deprotonation generates final product
3- seleno cumarin.
Compared with prior art, the invention has the following advantages that
The method of the present invention has synthesized 3- seleno perfume using cumarin and selenide as raw material, by regioselectivity selenizing for the first time
Beans chlorins compound.Reaction raw materials are cheap and easy to get, and preparation method is simple；It is cheap and easy to get using PIFA as oxidant, thus react at
This is low.It reacts and is carried out in air atmosphere at room temperature, therefore is easy to operate.Reaction time is short, and yield is high.The method of the present invention can fit
For synthesizing different types of 3- seleno coumarin kind compound.
Specific embodiment
Below with reference to embodiment, the present invention will be described in detail, but the present invention is not limited to this.
Embodiment 1
Cumarin (0.2mmol), 1,2- hexichol diselenide (0.4 mmol), PIFA are separately added into the reaction flask of 4mL
(0.4mmol)、TMSN3(azidotrimethylsilane) (0.4mmol) and toluene (toluene) (2.0mL), is stirred at room temperature.TLC
Tracing detection reaction.After 12 hours, feedstock portions conversion.Water and methylene chloride are added in reaction system, separates organic layer.With two
Chloromethanes washes water layer twice, in conjunction with all organic layers, and is washed with water twice.Organic layer is dry with anhydrous sodium sulfate, concentration, column
Chromatography (10% ethyl acetate petroleum ether solution) obtains product 45.1mg, yield 75%, reaction process such as following formula institute
Show:
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(500MHz,DMSO-d6)δ7.70–7.68(m,2H),7.56–7.47(m, 5H),7.42(s,1H),
7.40 (d, J=8.3Hz, 1H), 7.29-7.25 (m, 1H) ppm；13C NMR (126MHz,DMSO-d6)δ158.46,151.91,
139.28,135.54,130.98,130.15, 129.37,127.14,125.54,124.63,124.03,119.31,
116.00ppm。
Embodiment 2
Cumarin (0.2mmol), 1,2- hexichol diselenide (0.4 mmol), PIFA are separately added into the reaction flask of 4mL
(0.4mmol)、TMSN3(0.4mmol) and MeCN (acetonitrile) (2.0mL), is stirred at room temperature.The reaction of TLC tracing detection.0.5 hour
Afterwards, raw material converts completely.Water and methylene chloride are added in reaction system, separates organic layer.Water layer is washed twice with methylene chloride,
In conjunction with all organic layers, and it is washed with water twice.Organic layer is dry with anhydrous sodium sulfate, concentration, column chromatography for separation (10% acetic acid
Ethyl ester petroleum ether solution), product 53.6mg is obtained, yield 89%, reaction process is shown below:
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(500MHz,DMSO-d6)δ7.70–7.68(m,2H),7.56–7.47(m, 5H),7.42(s,1H),
7.40 (d, J=8.3Hz, 1H), 7.29-7.25 (m, 1H) ppm；13C NMR (126MHz,DMSO-d6)δ158.46,151.91,
139.28,135.54,130.98,130.15, 129.37,127.14,125.54,124.63,124.03,119.31,
116.00ppm。
Embodiment 3
Cumarin (0.2mmol), 1,2- hexichol diselenide (0.4 mmol), PIFA are separately added into the reaction flask of 4mL
(0.4mmol)、TMSN3(0.4mmol) and DCM (2.0mL), is stirred at room temperature.The reaction of TLC tracing detection.After 0.5 hour, raw material
Conversion completely.Water and methylene chloride are added in reaction system, separates organic layer.Water layer is washed twice with methylene chloride, in conjunction with institute
There is organic layer, and is washed with water twice.Organic layer is dry with anhydrous sodium sulfate, concentration, column chromatography for separation (10% ethyl acetate stone
Oily ethereal solution), product 59.0mg is obtained, yield 98%, reaction process is shown below:
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(500MHz,DMSO-d6)δ7.70–7.68(m,2H),7.56–7.47(m, 5H),7.42(s,1H),
7.40 (d, J=8.3Hz, 1H), 7.29-7.25 (m, 1H) ppm；13C NMR (126MHz,DMSO-d6)δ158.46,151.91,
139.28,135.54,130.98,130.15, 129.37,127.14,125.54,124.63,124.03,119.31,
116.00ppm。
Embodiment 4
Cumarin (0.2mmol), 1,2- hexichol diselenide (0.4 mmol), PIFA are separately added into the reaction flask of 4mL
(0.4mmol) and DCM (2.0mL), is stirred at room temperature.The reaction of TLC tracing detection.After 0.5 hour, raw material converts completely.Reactant
Water and methylene chloride are added in system, separates organic layer.Water layer is washed twice with methylene chloride, in conjunction with all organic layers, and uses water
It washes twice.Organic layer is dry with anhydrous sodium sulfate, and concentration, column chromatography for separation (10% ethyl acetate petroleum ether solution) obtains
Product 56.6mg, yield 94%, reaction process is shown below:
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(500MHz,DMSO-d6)δ7.70–7.68(m,2H),7.56–7.47(m, 5H),7.42(s,1H),
7.40 (d, J=8.3Hz, 1H), 7.29-7.25 (m, 1H) ppm；13C NMR (126MHz,DMSO-d6)δ158.46,151.91,
139.28,135.54,130.98,130.15, 129.37,127.14,125.54,124.63,124.03,119.31,
116.00ppm。
Embodiment 5
Cumarin (0.2mmol), 1,2- hexichol diselenide (0.4 mmol), PIDA (two are separately added into the reaction flask of 4mL
Acetic acid iodobenzene) (0.4mmol) and DCM (2.0mL), it is stirred at room temperature.The reaction of TLC tracing detection.After 12 hours, reactionless generation.
Embodiment 6
Cumarin (0.2mmol), 1,2- hexichol diselenide (0.2 mmol), PIFA are separately added into the reaction flask of 4mL
(0.2mmol) and DCM (2.0mL), is stirred at room temperature.The reaction of TLC tracing detection.After 1 hour, raw material converts completely.Reaction system
Middle addition water and methylene chloride separate organic layer.Water layer is washed twice with methylene chloride, in conjunction with all organic layers, and is washed with water
Twice.Organic layer is dry with anhydrous sodium sulfate, and concentration, column chromatography for separation (10% ethyl acetate petroleum ether solution) is produced
Object 56.6mg, yield 94%, reaction process is shown below:
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(500MHz,DMSO-d6)δ7.70–7.68(m,2H),7.56–7.47(m, 5H),7.42(s,1H),
7.40 (d, J=8.3Hz, 1H), 7.29-7.25 (m, 1H) ppm；13C NMR (126MHz,DMSO-d6)δ158.46,151.91,
139.28,135.54,130.98,130.15, 129.37,127.14,125.54,124.63,124.03,119.31,
116.00ppm。
Embodiment 7
Cumarin (0.2mmol), 1,2- hexichol diselenide (0.24 mmol), PIFA are separately added into the reaction flask of 4mL
(0.2mmol) and DCM (2.0mL), is stirred at room temperature.The reaction of TLC tracing detection.After 1 hour, raw material converts completely.Reaction system
Middle addition water and methylene chloride separate organic layer.Water layer is washed twice with methylene chloride, in conjunction with all organic layers, and is washed with water
Twice.Organic layer is dry with anhydrous sodium sulfate, and concentration, column chromatography for separation (10% ethyl acetate petroleum ether solution) is produced
Object 57.2mg, yield 95%, reaction process is shown below:
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(500MHz,DMSO-d6)δ7.70–7.68(m,2H),7.56–7.47(m, 5H),7.42(s,1H),
7.40 (d, J=8.3Hz, 1H), 7.29-7.25 (m, 1H) ppm；13C NMR (126MHz,DMSO-d6)δ158.46,151.91,
139.28,135.54,130.98,130.15, 129.37,127.14,125.54,124.63,124.03,119.31,
116.00ppm。
Embodiment 8
4- methoxy coumarin (0.2mmol), 1,2- hexichol diselenide are separately added into the reaction flask of 4mL
(0.24mmol), PIFA (0.2mmol) and DCM (2.0mL), are stirred at room temperature.The reaction of TLC tracing detection.After 1 hour, raw material is complete
Full conversion.Water and methylene chloride are added in reaction system, separates organic layer.Water layer is washed twice with methylene chloride, in conjunction with all
Organic layer, and be washed with water twice.Organic layer is dry with anhydrous sodium sulfate, concentration, column chromatography for separation (17% ethyl acetate petroleum
Ethereal solution), product 60.9mg is obtained, yield 92%, reaction process is shown below:
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(500MHz,DMSO-d6) δ 7.83 (dd, J=8.0,1.5Hz, 1H), 7.70-7.67 (m, 1H), 7.45-
7.38(m,4H),7.29–7.21(m,3H),4.13(s,3H)ppm；13C NMR(126MHz,DMSO-d6)δ169.31,
160.67,152.69,133.14,130.79,129.99, 129.25,126.66,124.41,123.88,116.73,
116.33,102.82,61.82ppm。
Embodiment 9
Be separately added into the reaction flask of 4mL 6- nitro cumarin (0.2mmol), 1,2- hexichol diselenide (0.24mmol),
PIFA (0.2mmol) and DCM (2.0mL), is stirred at room temperature.The reaction of TLC tracing detection.After 24 hours, raw material converts completely.Instead
It answers and water and methylene chloride is added in system, separate organic layer.Water layer is washed twice with methylene chloride, in conjunction with all organic layers, and
It is washed with water twice.Organic layer is dry with anhydrous sodium sulfate, concentration, column chromatography for separation (20% ethyl acetate petroleum ether solution),
Product 57.5mg is obtained, yield 83%, reaction process is shown below:
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(600MHz,CDCl3) δ 8.28 (d, J=9.0Hz, 1H), 8.10 (s, 1H), 7.71 (d, J=7.1Hz,
2H), 7.56 (t, J=7.1Hz, 1H), 7.51 (t, J=7.2Hz, 2H), 7.43 (d, J=9.0Hz, 1H), 7.01 (s, 1H)
ppm；13C NMR(126MHz,CDCl3)δ157.93, 155.41,144.09,137.06,135.07,130.52,130.49,
130.33,124.81,124.51, 121.95,119.94,117.61ppm。
Embodiment 10
Be separately added into the reaction flask of 4mL 6- phenyl coumarin (0.2mmol), 1,2- hexichol diselenide (0.24mmol),
PIFA (0.2mmol) and DCM (2.0mL), is stirred at room temperature.The reaction of TLC tracing detection.After 1 hour, raw material converts completely.Reaction
Water and methylene chloride are added in system, separates organic layer.Water layer is washed twice with methylene chloride, in conjunction with all organic layers, is used in combination
Washing is twice.Organic layer is dry with anhydrous sodium sulfate, and concentration, column chromatography for separation (10% ethyl acetate petroleum ether solution) obtains
To product 71.7mg, yield 95%, reaction process is shown below:
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(600MHz,DMSO-d6) δ 7.86 (d, J=2.1Hz, 1H), 7.83 (dd, J=8.6,2.2Hz, 1H),
7.71-7.70 (m, 2H), 7.65 (d, J=7.3Hz, 2H), 7.56-7.49 (m, 4H), 7.46 (d, J=8.6Hz, 1H), 7.43
(t, J=7.7Hz, 2H), 7.35 (t, J=7.3Hz, 1H) ppm；13C NMR(151MHz,DMSO-d6)δ158.48,151.30,
139.01,138.35, 136.48,135.75,130.19,129.46,129.07,128.81,127.57,126.56,
125.33, 124.98,124.63,119.72,116.48ppm。
Embodiment 11
Be separately added into the reaction flask of 4mL 7- chlorocoumarin (0.2mmol), 1,2- hexichol diselenide (0.24mmol),
PIFA (0.2mmol) and DCM (2.0mL), is stirred at room temperature.The reaction of TLC tracing detection.After 1 hour, raw material converts completely.Reaction
Water and methylene chloride are added in system, separates organic layer.Water layer is washed twice with methylene chloride, in conjunction with all organic layers, is used in combination
Washing is twice.Organic layer is dry with anhydrous sodium sulfate, and concentration, column chromatography for separation (10% ethyl acetate petroleum ether solution) obtains
To product 65.1mg, yield 97%, reaction process is shown below:
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(600MHz,DMSO-d6) δ 7.69 (d, J=6.7Hz, 2H), 7.62 (s, 1H), 7.60 (d, J=
8.4Hz, 1H), 7..49-7.55 (m, 3H), 7.46 (s, 1H), 7.35 (dd, J=8.4,1.6Hz, 1H) ppm；13C NMR
(151MHz,DMSO-d6)δ158.03,152.32,138.58, 135.53,134.95,130.19,129.44,128.53,
125.39,124.85,124.39,118.41, 116.18ppm。
Embodiment 12
Be separately added into the reaction flask of 4mL 8- fluorine cumarin (0.2mmol), 1,2- hexichol diselenide (0.24mmol),
PIFA (0.2mmol) and DCM (2.0mL), is stirred at room temperature.The reaction of TLC tracing detection.After 2.5 hours, raw material converts completely.Instead
It answers and water and methylene chloride is added in system, separate organic layer.Water layer is washed twice with methylene chloride, in conjunction with all organic layers, and
It is washed with water twice.Organic layer is dry with anhydrous sodium sulfate, concentration, column chromatography for separation (10% ethyl acetate petroleum ether solution),
Product 60.0mg is obtained, yield 94%, reaction process is shown below:
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(500MHz,DMSO-d6) δ 7.71-7.69 (m, 2H), 7.56-7.49 (m, 4H), 7.44 (d, J=
1.2Hz, 1H), 7.36 (d, J=7.9Hz, 1H), 7.28-7.24 (m, 1H) ppm；13C NMR(126MHz,DMSO-d6)δ
157.41,148.32 (d, J=247.8Hz), 139.83 (d, J=11.7Hz), 138.56 (d, J=2.6Hz), 135.63,
(130.23,129.54,125.58,125.31,124.74 d, J=6.9Hz), 122.67 (d, J=3.5Hz), 121.30,
117.08 (d, J=17.1Hz) ppm；19F NMR(565MHz,DMSO-d6)δ-135.70ppm。
Embodiment 13
5,7- diformazan butylcoumariii (0.2mmol), 1,2- hexichol diselenide are separately added into the reaction flask of 4mL
(0.24mmol), PIFA (0.2mmol) and DCM (2.0mL), are stirred at room temperature.The reaction of TLC tracing detection.After 0.5 hour, raw material
Conversion completely.Water and methylene chloride are added in reaction system, separates organic layer.Water layer is washed twice with methylene chloride, in conjunction with institute
There is organic layer, and is washed with water twice.Organic layer is dry with anhydrous sodium sulfate, concentration, column chromatography for separation (10% ethyl acetate stone
Oily ethereal solution), product 64.5mg is obtained, yield 98%, reaction process is shown below:
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(600MHz,DMSO-d6)δ7.69–7.68(m,2H),7.53–7.48(m, 3H),7.46(s,1H),
7.07(s,1H),6.97(s,1H),2.33(s,3H),2.16(s,3H)ppm；13C NMR(151MHz,DMSO-d6)δ158.48,
152.72,141.70,137.13,135.21, 134.40,130.13,129.25,126.96,126.15,121.47,
115.65,114.14,21.05,17.27 ppm。
Embodiment 14
6,7- diacetoxy cumarin (0.2mmol), 1,2- hexichol diselenide are separately added into the reaction flask of 4mL
(0.24mmol), PIFA (0.2mmol) and DCM (2.0mL), are stirred at room temperature.The reaction of TLC tracing detection.After 1 hour, raw material is complete
Full conversion.Water and methylene chloride are added in reaction system, separates organic layer.Water layer is washed twice with methylene chloride, in conjunction with all
Organic layer, and be washed with water twice.Organic layer is dry with anhydrous sodium sulfate, concentration, column chromatography for separation (20% ethyl acetate petroleum
Ethereal solution), product 78.4mg is obtained, yield 94%, reaction process is shown below:
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(500MHz,DMSO-d6)δ7.70–7.68(m,2H),7.55(s,1H),7.52 –7.48(m,3H),
7.46(s,1H),7.42(s,1H),2.30(s,3H),2.27(s,3H)ppm；13C NMR(126MHz,DMSO-d6)δ168.16,
167.78,158.18,149.55,143.58,138.57, 138.21,135.52,130.18,129.39,125.48,
124.59,121.12,117.62,111.60,20.24, 20.10ppm。
Embodiment 15
2H- benzo [h] chromen-2-one (0.2mmol), 1,2- hexichol diselenide are separately added into the reaction flask of 4mL
(0.24mmol), PIFA (0.2mmol) and DCM (2.0mL), are stirred at room temperature.The reaction of TLC tracing detection.After 0.5 hour, raw material
Conversion completely.Water and methylene chloride are added in reaction system, separates organic layer.Water layer is washed twice with methylene chloride, in conjunction with institute
There is organic layer, and is washed with water twice.Organic layer is dry with anhydrous sodium sulfate, concentration, column chromatography for separation (10% ethyl acetate stone
Oily ethereal solution), product 63.9mg is obtained, yield 91%, reaction process is shown below:
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(500MHz,DMSO-d6)δ8.30–8.28(m,1H),7.98–7.95(m, 1H),7.73–7.70(m,
3H),7.69–7.65(m,2H),7.55–7.49(m,5H)ppm；13C NMR(126MHz,DMSO-d6)δ158.47,148.51,
140.27,135.48,133.71,130.22, 129.40,128.34,128.00,127.39,125.70,124.36,
123.57,123.56,121.89, 120.91,115.14ppm。
Embodiment 16
7,8,9,10- tetrahydro -2H- benzo [h] chromen-2-one (0.2 mmol), 1,2- are separately added into the reaction flask of 4mL
Hexichol diselenide (0.24mmol), PIFA (0.2mmol) and DCM (2.0mL), are stirred at room temperature.The reaction of TLC tracing detection.0.5 is small
Shi Hou, raw material convert completely.Water and methylene chloride are added in reaction system, separates organic layer.Water layer is washed two with methylene chloride
It is secondary, in conjunction with all organic layers, and it is washed with water twice.Organic layer is dry with anhydrous sodium sulfate, concentration, column chromatography for separation (10%
Ethyl acetate petroleum ether solution), product 69.6mg is obtained, yield 98%, reaction process is shown below:
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(600MHz,DMSO-d6) δ 7.65 (d, J=6.5Hz, 2H), 7.50-7.46 (m, 3H), 7.43 (s,
1H), 7.22 (d, J=8.0Hz, 1H), 6.99 (d, J=8.0Hz, 1H), 2.76 (t, J=6.2Hz, 4H), 1.78-1.71 (m,
4H)ppm；13C NMR(151MHz,DMSO-d6)δ 158.61,150.16,141.09,140.74,135.10,130.05,
129.10,126.03,125.24, 123.96,123.85,121.35,116.67,29.05,21.88,21.80,21.47ppm。
Embodiment 17
Be separately added into the reaction flask of 4mL cumarin (0.2mmol), 1,2- di-o-tolyl diselenide (0.24mmol),
PIFA (0.2mmol) and DCM (2.0mL), is stirred at room temperature.The reaction of TLC tracing detection.After 1.5 hours, raw material converts completely.Instead
It answers and water and methylene chloride is added in system, separate organic layer.Water layer is washed twice with methylene chloride, in conjunction with all organic layers, and
It is washed with water twice.Organic layer is dry with anhydrous sodium sulfate, concentration, column chromatography for separation (10% ethyl acetate petroleum ether solution),
Product 61.8mg is obtained, yield 98%, reaction process is shown below:
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(500MHz,DMSO-d6) δ 7.67 (d, J=7.4Hz, 1H), 7.56-7.53 (m, 1H), 7.51 (dd, J
=7.8,1.3Hz, 1H), 7.49-7.44 (m, 2H), 7.41 (d, J=8.2Hz, 1H), 7.30-7.25 (m, 2H), 7.19 (s,
1H),2.41(s,3H)ppm；13C NMR(126MHz, DMSO-d6)δ158.63,151.88,142.01,138.37,137.04,
130.92,130.25,127.56, 127.13,126.12,124.69,123.49,119.43,116.07,22.06ppm。
Embodiment 18
Be separately added into the reaction flask of 4mL cumarin (0.2mmol), bis- fluorophenyl diselenides (0.24mmol) of 1,2-,
PIFA (0.2mmol) and DCM (2.0mL), is stirred at room temperature.The reaction of TLC tracing detection.After 2 hours, raw material converts completely.Reaction
Water and methylene chloride are added in system, separates organic layer.Water layer is washed twice with methylene chloride, in conjunction with all organic layers, is used in combination
Washing is twice.Organic layer is dry with anhydrous sodium sulfate, and concentration, column chromatography for separation (10% ethyl acetate petroleum ether solution) obtains
To product 62.6mg, yield 98%, reaction process is shown below:
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(600MHz,DMSO-d6) δ 7.67 (s, 1H), 7.62 (d, J=7.7Hz, 1H), 7.60-7.54 (m,
2H), 7.53-7.50 (m, 2H), 7.43 (d, J=8.3Hz, 1H), 7.35-7.30 (m, 2H) ppm；13C NMR(151MHz,
DMSO-d6) δ 162.33 (d, J=248.4Hz), 158.60,152.33,141.42,131.89 (d, J=8.0Hz),
131.47,131.03 (d, J=2.0Hz), 128.01 (d, J=6.9Hz), 127.60,124.80,122.74,121.56 (d, J
=22.1Hz), 119.45,116.26 (d, J=21.0Hz), 116.15ppm；19F NMR(565MHz,DMSO-d6)δ -
110.85ppm。
Embodiment 19
Cumarin (0.2mmol), bis- m-nitro base diselenide of 1,2- are separately added into the reaction flask of 4mL
(0.24mmol), PIFA (0.2mmol) and DCM (2.0mL), are stirred at room temperature.The reaction of TLC tracing detection.After 12 hours, raw material
Conversion completely.Water and methylene chloride are added in reaction system, separates organic layer.Water layer is washed twice with methylene chloride, in conjunction with institute
There is organic layer, and is washed with water twice.Organic layer is dry with anhydrous sodium sulfate, concentration, column chromatography for separation (20% ethyl acetate stone
Oily ethereal solution), product 61.6mg is obtained, yield 89%, reaction process is shown below:
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(500MHz,DMSO-d6) δ 8.43-8.42 (m, 1H), 8.31-8.29 (m, 1H), 8.09 (d, J=
7.8Hz, 1H), 7.83 (s, 1H), 7.73 (t, J=8.0Hz, 1H), 7.63-7.58 (m, 2H), 7.43 (d, J=8.2Hz,
1H), 7.32 (t, J=7.5Hz, 1H) ppm；13C NMR(126 MHz,DMSO-d6)δ158.44,152.42,148.30,
142.49,140.92,131.56,131.20, 128.86,128.44,127.67,124.66,123.70,121.91,
119.38,116.08ppm。
Embodiment 20
Be separately added into the reaction flask of 4mL cumarin (0.2mmol), bis- p-bromophenyl diselenide (0.24mmol) of 1,2-,
PIFA (0.2mmol) and DCM (2.0mL), is stirred at room temperature.The reaction of TLC tracing detection.After 1.5 hours, raw material converts completely.Instead
It answers and water and methylene chloride is added in system, separate organic layer.Water layer is washed twice with methylene chloride, in conjunction with all organic layers, and
It is washed with water twice.Organic layer is dry with anhydrous sodium sulfate, concentration, column chromatography for separation (10% ethyl acetate petroleum ether solution),
Product 73.7mg is obtained, yield 97%, reaction process is shown below:
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(500MHz,DMSO-d6)δ7.68–7.65(m,2H),7.63–7.60(m, 3H),7.59(s),7.59–
7.55 (m, 1H), 7.42 (d, J=8.2Hz, 1H), 7.30 (td, J=7.6,1.0Hz, 1H) ppm；13C NMR(126MHz,
DMSO-d6)δ158.49,152.09,140.30, 137.31,133.03,131.22,127.46,125.14,124.69,
123.25,123.06,119.42, 116.06ppm。
Embodiment 21
Cumarin (0.2mmol), 1,2- bis- (naphthalene -2- base) diselenide are separately added into the reaction flask of 4mL
(0.24mmol), PIFA (0.2mmol) and DCM (2.0mL), are stirred at room temperature.The reaction of TLC tracing detection.After 12 hours, raw material portion
Divide conversion.Water and methylene chloride are added in reaction system, separates organic layer.Water layer is washed twice with methylene chloride, in conjunction with all
Organic layer, and be washed with water twice.Organic layer is dry with anhydrous sodium sulfate, concentration, column chromatography for separation (10% ethyl acetate petroleum
Ethereal solution), product 42.2mg is obtained, yield 60%, reaction process is shown below:
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(600MHz,DMSO-d6) δ 8.34 (s, 1H), 8.02-7.99 (m, 3H), 7.71 (d, J=8.4Hz,
1H), 7.63-7.58 (m, 2H), 7.54 (t, J=7.8Hz, 1H), 7.50 (d, J=6.9Hz, 1H), 7.50 (s, 1H), 7.41
(d, J=8.3Hz, 1H), 7.24 (t, J=7.5Hz, 1H) ppm；13C NMR(151MHz,DMSO-d6)δ158.57,151.98,
139.53,135.34,133.73, 132.73,131.82,131.01,129.63,127.78,127.74,127.27,
127.22,126.81, 124.63,124.09,122.97,119.44,116.03ppm。
Embodiment 22
Cumarin (0.2mmol), 1,2- bis- (2- methoxypyridine -3- base) diselenide are separately added into the reaction flask of 4mL
(0.24mmol), PIFA (0.2mmol) and DCM (2.0mL), are stirred at room temperature.The reaction of TLC tracing detection.After 1 hour, raw material is complete
Full conversion.Water and methylene chloride are added in reaction system, separates organic layer.Water layer is washed twice with methylene chloride, in conjunction with all
Organic layer, and be washed with water twice.Organic layer is dry with anhydrous sodium sulfate, concentration, column chromatography for separation (17% ethyl acetate petroleum
Ethereal solution), product 53.8mg is obtained, yield 81%, reaction process is shown below:
Nuclear magnetic resonance spectroscopy is carried out to the product that the present embodiment is prepared:
1H NMR(600MHz,DMSO-d6) δ 8.24 (d, J=3.5Hz, 1H), 7.89-7.87 (m, 1H), 7.84 (s,
1H), 7.68 (d, J=7.7Hz, 1H), 7.61 (t, J=7.3Hz, 1H), 7.44 (d, J=8.3Hz, 1H), 7.34 (t, J=
7.5Hz,1H),7.03–7.01(m,1H),3.91(s,3H)ppm；13C NMR(151MHz,DMSO-d6)δ161.52,158.67,
152.67,147.19,143.93, 143.81,131.70,127.74,124.79,119.70,119.48,118.44,
116.18,110.79,54.01 ppm。
Claims (7)
1. a kind of preparation method of 3- seleno coumarin kind compound, which is characterized in that in a solvent, with two (trifluoroacetyl oxygen
Base) iodobenzene is oxidant, coumarin kind compound and selenide compounds are reacted, after reaction after post treatment
To the 3- seleno cumarin；
Shown in the structure such as formula (I) of the 3- seleno cumarin:
Shown in the structure of the coumarin kind compound such as formula (II):
Shown in the structure of the selenide compounds such as formula (III):
In formula (I)~(III), R1Hydrogen, C1~C4Alkyl, C1~C4Alkoxy, acyloxy, nitro, phenyl or halogen；
R2For hydrogen, C1~C4Alkyl, C1~C4Alkoxy, nitro or halogen；
X is N or C；
The representation of dotted portion may exist, can partially in the presence of or be completely absent.
2. the preparation method of 3- seleno coumarin kind compound as described in claim 1, which is characterized in that the 3- seleno
The structure of coumarin kind compound such as formula (IV)~(IX) is shown in any one:
In formula (IV), R1For hydrogen, C1~C4Alkyl, C1~C4Alkoxy, acyloxy, nitro, phenyl or halogen；R2For hydrogen, C1~C4
Alkyl, C1~C4Alkoxy, nitro or halogen；
Shown in the structure of the coumarin kind compound such as formula (X)~(XII):
In formula (X), R1For hydrogen, C1~C4Alkyl, C1~C4Alkoxy, acyloxy, nitro, phenyl or halogen；
The selenide compounds have the structure of chemical formula (XIII)~(XV):
In formula (XIII), R2For hydrogen, C1~C4Alkyl, C1~C4Alkoxy, nitro or halogen.
3. the preparation method of 3- seleno coumarin kind compound as described in claim 1, which is characterized in that R1For hydrogen, methyl,
Methoxyl group, acetoxyl group, nitro, phenyl, F, Cl or Br.
4. the preparation method of 3- seleno coumarin kind compound as described in claim 1, which is characterized in that R2For hydrogen, methyl,
Methoxyl group, nitro, F, Cl or Br.
5. the preparation method of 3- seleno coumarin kind compound as described in claim 1, which is characterized in that reaction temperature 24
~26 DEG C, the reaction time is 0.5~12h.
6. the preparation method of 3- seleno coumarin kind compound as described in claim 1, which is characterized in that the cumarin
The molar ratio of class compound and the selenide compounds is 1:1.1~1.3；The coumarin kind compound and described
The molar ratio of two (trifluoroacetyl oxygroup) iodobenzenes is 1:0.9~1.1.
7. the preparation method of 3- seleno coumarin kind compound as described in claim 1, which is characterized in that the solvent is
DCM (methylene chloride).
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